CN113272249A - Fibrous carbon nanostructure, method for producing fibrous carbon nanostructure, and method for producing surface-modified fibrous carbon nanostructure - Google Patents

Fibrous carbon nanostructure, method for producing fibrous carbon nanostructure, and method for producing surface-modified fibrous carbon nanostructure Download PDF

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CN113272249A
CN113272249A CN202080007795.2A CN202080007795A CN113272249A CN 113272249 A CN113272249 A CN 113272249A CN 202080007795 A CN202080007795 A CN 202080007795A CN 113272249 A CN113272249 A CN 113272249A
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fibrous carbon
carbon nanostructure
temperature
peak
height
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CN113272249B (en
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川上修
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Zeon Corp
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/02—Single-walled nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC

Abstract

The purpose of the present invention is to provide a fibrous carbon nanostructure that can be easily subjected to a surface modification treatment. The fibrous carbon nanostructure of the present invention has a temperature differential curve in which the half-peak width of the peak is 38 ℃ or more and less than 90 ℃, the temperature differential curve is a first differential curve of a thermogravimetric curve obtained by thermogravimetric analysis in a dry air environment, and the high-temperature side temperature at the height of 1/10 of the peak top is 658 ℃ or more.

Description

Fibrous carbon nanostructure, method for producing fibrous carbon nanostructure, and method for producing surface-modified fibrous carbon nanostructure
Technical Field
The present invention relates to a fibrous carbon nanostructure, a method for producing a fibrous carbon nanostructure, and a method for producing a surface-modified fibrous carbon nanostructure.
Background
In recent years, a fibrous carbon nanostructure such as a carbon nanotube (hereinafter, sometimes referred to as "CNT") has attracted attention as a material excellent in electrical conductivity, thermal conductivity, and mechanical properties.
However, since a fibrous carbon nanostructure such as CNT is easily formed into a bundle structure by van der waals force or the like, it is difficult to disperse the fibrous carbon nanostructure in a solvent or a resin, and thus it is difficult to exhibit desired high characteristics.
Therefore, the following techniques are proposed: the dispersibility of the fibrous carbon nanostructure is improved by subjecting the fibrous carbon nanostructure such as CNT to a surface modification treatment such as an oxidation treatment (for example, see patent document 1).
Documents of the prior art
Patent document
Patent document 1: international publication No. 2015/045418.
Disclosure of Invention
Problems to be solved by the invention
Here, from the viewpoint of obtaining a surface-modified fibrous carbon nanostructure having excellent dispersibility by surface modification treatment of the fibrous carbon nanostructure, it is required to perform surface modification treatment well on the fibrous carbon nanostructure as a raw material.
However, conventional fibrous carbon nanostructures still have room for improvement in terms of further improving the ease of surface modification treatment.
Accordingly, an object of the present invention is to provide a fibrous carbon nanostructure which can be easily subjected to a surface modification treatment, and a method for producing the same.
Further, an object of the present invention is to provide a surface-modified fibrous carbon nanostructure which is subjected to a surface modification treatment favorably.
Means for solving the problems
The present inventors have conducted intensive studies in order to achieve the above object. Then, the present inventors have found that a fibrous carbon nanostructure having a predetermined property is easily surface-modified, and have completed the present invention.
That is, the present invention has an object to advantageously solve the above-mentioned problems, and the fibrous carbon nanostructure of the present invention is characterized in that a half-width of a peak of a temperature differential curve (hereinafter, the "temperature differential curve of the first differential curve as a thermogravimetric curve" is simply referred to as "temperature differential curve") which is a first order differential curve of a thermogravimetric curve obtained by thermogravimetric analysis in a dry air environment is 38 ℃ or more and less than 90 ℃, and a high-temperature side temperature at a height of 1/10 of a peak top height of the peak is 658 ℃ or more. A fibrous carbon nanostructure having a peak of a temperature differential curve with a half-value width of 38 ℃ or more and less than 90 ℃ and a high-temperature side temperature of 658 ℃ or more at a height of 1/10 of the peak top height is easily subjected to surface modification such as oxidation treatment.
Here, in the present invention, "peak" means: in a graph of the temperature differential curve (e.g., fig. 1), a point (e.g., DTG in fig. 1) including a point at which the absolute value of the weight change rate per 1 ℃ is maximum in a convex curve portion including a point at which the absolute value of the weight change rate per 1 ℃ is maximummax) In the convex curve portion of (a), the temperature on the low temperature side (for example, T in fig. 1) of the point where the absolute value of the weight change rate per 1 ℃ is a minimum value (minimum value in the case where the one protrusion (maximum value) is one and there is no minimum value as shown in fig. 1)ini) And the portion of the curve between the high temperature side temperature and the temperature. Here, the point at which the absolute value of the weight change rate per 1 ℃ is a minimum value (minimum value in the case where one projection (maximum value) is shown in fig. 1 and there is no minimum value) is the height of 1/10 or less of the peak top height of the peak. The "half width of the peak" and the "high temperature side temperature at 1/10 height of the peak top height" can be determined by the method described in the examples of the present specificationAnd (6) discharging.
In the fibrous carbon nanostructure of the present invention, the weight reduction rate of the low-temperature side temperature at a height of 7.5/10 of the peak top height of the peak is preferably 40 wt% or less. The fibrous carbon nanostructure having a weight reduction rate at a low-temperature side temperature of 40 wt% or less at a height of 7.5/10 of the peak top height of the peak is easily subjected to surface modification treatment such as oxidation treatment.
In the present invention, the "weight reduction rate at a low temperature side temperature at a height of 7.5/10 of the peak top height of the peak" can be determined by the method described in the examples of the present specification.
In the fibrous carbon nanostructure of the present invention, the peak top temperature of the peak is preferably 530 ℃ or higher and less than 730 ℃. The fibrous carbon nanostructure having a peak top temperature of less than 530 ℃ is easily burned when subjected to surface treatment modification such as oxidation treatment, while the fibrous carbon nanostructure having a peak top temperature of 730 ℃ or more is hardly subjected to surface modification when subjected to surface treatment modification such as oxidation treatment.
In the present invention, the "peak top temperature of the peak" can be determined by the method described in the examples of the present specification.
The present invention is also directed to solving the above-mentioned problems, and a method for producing a fibrous carbon nanostructure of the present invention is a method for producing a fibrous carbon nanostructure that produces any one of the above-mentioned fibrous carbon nanostructures, and is characterized by comprising a step of heating the fibrous carbon nanostructure to a temperature of 120 ℃ or higher in a vacuum environment.
The present invention is also directed to a method for producing a fibrous carbon nanostructure, which is a method for producing a fibrous carbon nanostructure that produces any one of the above fibrous carbon nanostructures, and is characterized by comprising a step of heating the fibrous carbon nanostructure to a temperature of 800 ℃ or higher in an inert gas atmosphere.
The method for producing a surface-modified fibrous carbon nanostructure of the present invention is characterized by comprising a step of subjecting any one of the above-described fibrous carbon nanostructures to a surface modification treatment to obtain a surface-modified fibrous carbon nanostructure. Here, the surface modification treatment may be a wet oxidation treatment.
Effects of the invention
According to the present invention, a fibrous carbon nanostructure that can be easily subjected to surface modification treatment and a method for producing the same can be provided.
Further, according to the present invention, a method for producing a surface-modified fibrous carbon nanostructure, which is surface-modified satisfactorily, can be provided.
Drawings
Fig. 1 is a diagram schematically showing the shape of the peak of the temperature differential curve.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
Here, the fibrous carbon nanostructure of the present invention is easily subjected to surface modification treatment such as oxidation treatment. The surface-modified fibrous carbon nanostructure obtained by subjecting the fibrous carbon nanostructure of the present invention to a surface modification treatment is not particularly limited, and can be used, for example, in the preparation of a dispersion liquid in which the surface-modified fibrous carbon nanostructure is dispersed in a dispersion medium.
(fibrous carbon nanostructure)
The fibrous carbon nanostructure of the present invention requires that the half-peak width of the peak of the temperature differential curve obtained by thermogravimetric analysis in a dry air environment is 38 ℃ or more and less than 90 ℃, and that the high-temperature side temperature at the height of 1/10% of the peak top height of the peak is 658 ℃ or more. Further, the fibrous carbon nanostructure of the present invention has a half-value width of a peak of a temperature differential curve of 38 ℃ or more and less than 90 ℃ and a high-temperature side temperature at a height of 1/10 which is a peak top height of 658 ℃ or more, and therefore, is favorably surface-modified when subjected to a surface modification treatment such as an oxidation treatment.
Here, the fibrous carbon nanostructure is not particularly limited, and examples thereof include a carbon nanostructure having a cylindrical shape such as a Carbon Nanotube (CNT) and a carbon nanostructure having a non-cylindrical shape such as a carbon nanostructure in which a six-membered ring network of carbon is formed in a flat cylindrical shape.
The fibrous carbon nanostructure of the present invention may contain one kind of the above-described carbon nanostructure alone, or may contain two or more kinds.
Among the above, the fibrous carbon nanostructure preferably includes CNT. This is because the fibrous carbon nanostructure including CNTs can exhibit particularly excellent characteristics (for example, electrical conductivity, thermal conductivity, strength, and the like) when the dispersibility is improved by the surface modification treatment.
The fibrous carbon nanostructure containing the CNT may be formed of only the CNT, or may be a mixture of the CNT and a fibrous carbon nanostructure other than the CNT.
The CNTs in the fibrous carbon nanostructure are not particularly limited, and a single-walled carbon nanotube and/or a multi-walled carbon nanotube can be used, and the CNTs are preferably single-walled to 5-walled carbon nanotubes, and more preferably single-walled carbon nanotubes. This is because the smaller the number of carbon nanotube layers, the more excellent the properties can be exhibited when the dispersibility is improved by the surface modification treatment.
Here, the half-width of the peak of the temperature differential curve obtained by thermogravimetric analysis in a dry air environment of the fibrous carbon nanostructure of the present invention needs to be 38 ℃ or more and less than 90 ℃, and the half-width of the peak of the temperature differential curve of the fibrous carbon nanostructure is preferably 40 ℃ or more, and more preferably 49 ℃ or less. The half-width of the peak of the temperature differential curve of the fibrous carbon nanostructure is preferably 85 ℃ or less, and more preferably 80 ℃ or less. If the half-width of the peak of the temperature differential curve is not less than the lower limit of the preferred range, impurities that promote air oxidation can be removed, and if the half-width of the peak of the temperature differential curve is not more than the upper limit of the preferred range, burnout of the fibrous carbon nanostructure at the time of surface modification can be suppressed.
In addition, the high-temperature side temperature at 1/10 height of the peak top height of the temperature differential curve of the fibrous carbon nanostructure obtained by thermogravimetric analysis in a dry air environment of the present invention needs to be 658 ℃ or higher, and the high-temperature side temperature at 1/10 height of the peak top height of the temperature differential curve of the fibrous carbon nanostructure is preferably 660 ℃ or higher, more preferably 665 ℃ or higher, further preferably 673 ℃ or higher, further preferably 689 ℃ or higher, and usually 760 ℃ or lower. When the high-temperature side temperature at the height 1/10 of the peak top height of the peak of the temperature differential curve is equal to or higher than the lower limit of the preferable range, the surface modification treatment such as oxidation treatment can be performed more favorably.
In addition, the fibrous carbon nanostructure of the present invention preferably has a weight reduction rate of 40 wt% or less, more preferably 38 wt% or less, further preferably 35 wt% or less, further preferably 31 wt% or less, further preferably 29 wt% or less, and usually 10 wt% or more at a low temperature side at a height of 7.5/10 of the peak top height of a temperature differential curve obtained by thermogravimetric analysis in a dry air environment. When the weight reduction rate at the low temperature side temperature at a height of 7.5/10 of the peak top height of the peak of the temperature differential curve is not more than the above upper limit, surface modification can be more favorably performed when surface modification treatment such as oxidation treatment is performed.
Further, the fibrous carbon nanostructure of the present invention preferably has a peak top temperature of a peak of a temperature differential curve obtained by thermogravimetric analysis in a dry air environment of 530 ℃ or more, more preferably 550 ℃ or more, further preferably 570 ℃ or more, and further preferably less than 730 ℃, more preferably 710 ℃ or less, further preferably 690 ℃ or less. When the peak top temperature of the peak of the temperature differential curve is 530 ℃ or more and less than 730 ℃, the surface can be more favorably surface-modified when the surface modification treatment such as oxidation treatment is performed.
The thermogravimetric curve is a thermogravimetric curve in which the ordinate represents mass and the abscissa represents temperature, and the first differential curve of the thermogravimetric curve is a temperature differential curve in which the ordinate represents Differential Thermogravimetry (DTG) and the abscissa represents temperature.
Then, (i) the half-value width (c) of the peak of the temperature differential curve of the fibrous carbon nanostructure, (ii) the high-temperature side temperature at the height of 1/10 (the "b value" in table 1) (c) of the peak top height, (iii) the weight reduction rate (wt%) in the low-temperature side temperature at the height of 7.5/10 of the peak top height of the peak, and (iv) the peak top temperature (c) can be adjusted by changing the pretreatment conditions of the fibrous carbon nanostructure (for example, the environment at the time of pretreatment (vacuum environment or inert gas environment), the treatment temperature, and the like).
The average diameter of the fibrous carbon nanostructure is preferably 1nm or more, preferably 60nm or less, more preferably 30nm or less, and still more preferably 10nm or less. The fibrous carbon nanostructure having an average diameter within the above range can exhibit particularly excellent characteristics when the dispersibility is improved by the surface modification treatment.
Here, in the present invention, the "average diameter of the fibrous carbon nanostructures" can be obtained by measuring the diameter (outer diameter) of 20 fibrous carbon nanostructures selected at random on a Transmission Electron Microscope (TEM) image, and calculating the number average value.
In addition, as the fibrous carbon nanostructure, a fibrous carbon nanostructure in which the ratio (3 σ/Av) of the value (3 σ) obtained by multiplying the standard deviation (σ: sample standard deviation) of the diameter by 3 to the average diameter (Av) exceeds 0.20 and is less than 0.80 is preferably used, a fibrous carbon nanostructure in which 3 σ/Av exceeds 0.25 is more preferably used, and a fibrous carbon nanostructure in which 3 σ/Av exceeds 0.50 is further preferably used. The fibrous carbon nanostructure having a 3 σ/Av ratio of more than 0.20 and less than 0.80 can exhibit particularly excellent characteristics when the dispersibility is improved by the surface modification treatment.
The average diameter (Av) and the standard deviation (σ) of the fibrous carbon nanostructure can be adjusted by changing the production method and the production conditions of the fibrous carbon nanostructure, or by combining a plurality of fibrous carbon nanostructures obtained by different production methods.
Further, the fibrous carbon nanostructure has an average length of preferably 10 μm or more, more preferably 50 μm or more, further preferably 80 μm or more, preferably 600 μm or less, more preferably 550 μm or less, and further preferably 500 μm or less. The fibrous carbon nanostructure having an average length within the above range can exhibit particularly excellent characteristics when the dispersibility is improved by the surface modification treatment.
In the present invention, the "average length of the fibrous carbon nanostructures" can be determined by measuring the length of, for example, 20 fibrous carbon nanostructures on a Scanning Electron Microscope (SEM) image and calculating the number average value.
Here, the aspect ratio of the fibrous carbon nanostructure is usually more than 10. The aspect ratio of the fibrous carbon nanostructure can be determined by measuring the diameter and length of 20 randomly selected fibrous carbon nanostructures using a scanning electron microscope or a transmission electron microscope, and calculating the average value of the ratio of the diameter to the length (length/diameter).
Further, the BET specific surface area of the fibrous carbon nanostructure is preferably 600m2A value of at least one of,/g, more preferably 800m2A ratio of the total amount of the components to the total amount of the components is 2000m or more2A ratio of the total amount of the compound to the total amount of the compound is 1800m or less2(ii) less than g, more preferably 1600m2The ratio of the carbon atoms to the carbon atoms is less than g. If the fibrous carbon nanostructure has a BET specific surface area of 600m2When the surface modification treatment is carried out to improve the dispersibility, the resin composition can exhibit particularly excellent properties. Further, if the fibrous carbon nanostructure has a BET specific surface area of 2000m2When the amount is not more than g, the dispersibility can be sufficiently improved in the surface modification treatment.
In the present invention, the "BET specific surface area" refers to a nitrogen adsorption specific surface area measured by the BET method.
It is preferable that the fibrous carbon nanostructure is not subjected to the opening treatment, and shows a convex shape from a t-curve obtained from the adsorption isotherm. the fibrous carbon nanostructure having a shape with a t-curve that is convex upward can exhibit particularly excellent characteristics when the dispersibility is improved by the surface modification treatment.
The "t-curve" can be obtained by converting the relative pressure into the average thickness t (nm) of the nitrogen-adsorbing layer in the adsorption isotherm of the fibrous carbon nanostructure measured by the nitrogen adsorption method. That is, the t-curve of the fibrous carbon nanostructure can be obtained by obtaining the average thickness t of the nitrogen adsorbing layer corresponding to the relative pressure from a known standard isotherm obtained by plotting the average thickness t of the nitrogen adsorbing layer against the relative pressure P/P0 and performing the above-described conversion (t-curve method by de Boer et al).
In the present specification, the "t-curve" can be obtained by the method described in the examples of the present specification.
Here, in the substance having fine pores on the surface, the growth of the nitrogen adsorption layer is classified into the following processes (1) to (3). Further, the slope of the t-curve changes due to the following processes (1) to (3).
(1) Process for forming monomolecular adsorption layer of nitrogen molecules to whole surface
(2) Capillary condensation filling process for forming multi-molecule adsorption layer and following its fine hole
(3) Process for forming a multi-molecular adsorption layer to an apparent non-porous surface having pores filled with nitrogen
Further, with respect to the t-curve showing the upwardly convex shape, in the region where the average thickness t of the nitrogen adsorbing layer is small, when t becomes larger as compared with the case where the curve is located on the straight line passing through the origin, the curve becomes a position shifted downward from the straight line. The fibrous carbon nanostructure having the t-curve shape shows: the fibrous carbon nanostructure has a large ratio of the internal specific surface area to the total specific surface area, and a plurality of openings are formed in the carbon nanostructure constituting the fibrous carbon nanostructure.
The bending point of the t-curve of the fibrous carbon nanostructure is preferably in the range of 0.2. ltoreq. t (nm). ltoreq.1.5, more preferably in the range of 0.45. ltoreq. t (nm). ltoreq.1.5, and still more preferably in the range of 0.55. ltoreq. t (nm). ltoreq.1.0. When the bending point of the t-curve of the fibrous carbon nanostructure is within this range, particularly excellent characteristics can be exhibited when the dispersibility is improved by the surface modification treatment.
The "position of the bending point" is an intersection of the approximate straight line a in the process (1) and the approximate straight line B in the process (3).
Further, the fibrous carbon nanostructure preferably has a ratio of the internal specific surface area S2 to the total specific surface area S1 (S2/S1) of 0.05 to 0.30, which is obtained from the t-curve. When the S2/S1 value of the fibrous carbon nanostructure is within this range, particularly excellent characteristics can be exhibited when the dispersibility is improved by the surface modification treatment.
The total specific surface area S1 and the internal specific surface area S2 of the fibrous carbon nanostructure can be determined from the t-curve. Specifically, first, the total specific surface area S1 can be obtained from the slope of the approximate straight line in the process (1), and the external specific surface area S3 can be obtained from the slope of the approximate straight line in the process (3). Then, by subtracting the external specific surface area S3 from the total specific surface area S1, the internal specific surface area S2 can be calculated.
The measurement of the adsorption isotherm of the fibrous carbon nanostructure, the preparation of a t-curve, and the calculation of the total specific surface area S1 and the internal specific surface area S2 based on the analysis of the t-curve can be performed using, for example, "BELSORP (registered trademark) -mini" (manufactured by microtrac bel corp., ltd.) as a commercially available measurement apparatus.
Further, as the fibrous carbon nanostructure, a fibrous carbon nanostructure including a preferable CNT preferably has a peak of Radial Breathing Mode (RBM) when evaluated by raman spectroscopy. In addition, in the raman spectrum of a fibrous carbon nanostructure formed only of three or more layers of carbon nanotubes, RBM is not present.
In addition, the fibrous carbon nanostructure containing CNTs preferably has a ratio of G band peak intensity to D band peak intensity (G/D ratio) in a raman spectrum of 0.5 or more and 5.0 or less. When the G/D ratio is 0.5 or more and 5.0 or less, particularly excellent characteristics can be exhibited when the dispersibility is improved by the surface modification treatment.
In the present specification, the "G/D ratio" can be obtained by the following method.
< G/D ratio >
The fibrous carbon nanostructure near the center portion of the substrate was measured using a micro laser raman system (manufactured by Thermo Fisher Scientific, inc., nicolett almega XR).
The carbon purity of the fibrous carbon nanostructure is preferably 98 mass% or more, more preferably 99 mass% or more, and still more preferably 99.9 mass% or more.
In the present specification, the "carbon purity" can be determined by the following method.
< purity of carbon >
The carbon purity (weight reduced by combustion until 800 ℃ is reached) × 100 (%) was determined from the weight reduction when the fibrous carbon nanostructure was heated to 800 ℃ in air using a thermogravimetric analyzer (TG).
< pretreatment >
The pretreatment may include (i) a step of heating the fibrous carbon nanostructure to a temperature of 120 ℃ or higher, preferably 190 ℃ or higher (usually 300 ℃ or lower) in a vacuum atmosphere, or (ii) a step of heating the fibrous carbon nanostructure to a temperature of 800 ℃ or higher, preferably 900 ℃ or higher (usually 1100 ℃ or lower) in an inert gas atmosphere, but preferably includes a step of heating in a vacuum atmosphere.
By setting the treatment temperature to a temperature not lower than the lower limit, the surface of the fibrous carbon nanostructure can be more easily modified when the surface modification treatment such as oxidation treatment is performed, and by setting the treatment temperature to a temperature not higher than the upper limit, burning of the fibrous carbon nanostructure can be suppressed.
As the inert gas, for example, nitrogen, argon, helium, and the like are preferable.
The step (i) of heating the fibrous carbon nanostructure to 120 ℃ or higher in a vacuum atmosphere may be followed by the step (ii) of heating the fibrous carbon nanostructure to 800 ℃ or higher in an inert gas atmosphere, or the step (i) of heating the fibrous carbon nanostructure to 120 ℃ or higher in a vacuum atmosphere may be followed by the step (ii) of heating the fibrous carbon nanostructure to 800 ℃ or higher in an inert gas atmosphere.
The treatment time for the pretreatment is preferably 10 minutes or more, more preferably 1 hour or more, further preferably 3 hours or more, preferably 36 hours or less, more preferably 30 hours or less, and further preferably 24 hours or less.
By setting the treatment time to the lower limit or more, impurities that promote air oxidation can be removed, and by setting the treatment time to the upper limit or less, burnout of the fibrous carbon nanostructure can be suppressed.
(method for producing surface-modified fibrous carbon nanostructure)
In the method for producing a surface-modified fibrous carbon nanostructure of the present invention, a surface-modified fibrous carbon nanostructure having the above-described predetermined properties is subjected to a surface modification treatment to obtain a surface-modified fibrous carbon nanostructure.
< surface modification treatment >
The surface modification treatment is not particularly limited, and for example, nitric acid, sulfuric acid, or a mixed acid of nitric acid and sulfuric acid; surface modifying agents such as ozone, fluorine gas, and hydrogen peroxide. Among these, from the viewpoint of obtaining a surface-modified fibrous carbon nanostructure having excellent dispersibility, the surface modification treatment is preferably a wet oxidation treatment using nitric acid, sulfuric acid, or a mixed acid of nitric acid and sulfuric acid, and more preferably a wet oxidation treatment using a mixed acid of nitric acid and sulfuric acid. The surface modification treatment conditions can be set according to the type of the surface modification treatment agent used and the desired properties of the surface-modified fibrous carbon nanostructure.
< surface-modified fibrous carbon nanostructure >
The surface-modified fibrous carbon nanostructure obtained by subjecting the fibrous carbon nanostructure of the present invention to a surface modification treatment is not particularly limited, and can be dispersed in a dispersion medium such as water satisfactorily without using a dispersant. The obtained fibrous carbon nanostructure dispersion liquid can be used for the production of various molded articles (for example, antistatic films, transparent conductive films, and the like).
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following, unless otherwise specified, "%" representing the amount is based on mass.
In examples and comparative examples, (I) the half-width (c) of the peak of the temperature differential curve of (I) the fibrous carbon nanostructure including the CNT, (II) the high-temperature-side temperature (b value) at the height of 1/10 (c) the peak top height, (iii) the weight reduction rate (weight%) of the low-temperature-side temperature at the height of 7.5/10 of the peak top height, and (iv) the peak top temperature (c), and (II) the surface modification treatability were measured or evaluated by the following methods, respectively.
< temperature differential curve >
Using a thermogravimetric differential thermal synchrony measurement device (manufactured by BrukerAXS, product name "TG-DTA 2020 SA"), 2.00mg of the measurement sample was placed on a Pt disk (100. mu.L) of the thermogravimetric differential thermal synchrony measurement device, and the thermogravimetric curve (data acquisition frequency: 0.5 sec/point) of the fibrous carbon nanostructure was measured at a temperature rise rate of 5 ℃/min and a dry air flow rate of 200 mL/min, to obtain a temperature differential curve as a first differential curve (first differential curve preparation condition: differential width 10 points).
Here, the vertical axis of the thermogravimetric curve is mass, the horizontal axis is temperature, and the vertical axis of the temperature differential curve is Differential Thermogravimetric (DTG) and the horizontal axis is temperature, for example, as shown in fig. 1.
In FIG. 1, the peaks shown by the solid lines are the peaks before pretreatment (for example, comparative examples 1 to 4), and the peaks shown by the broken lines are the peaks after pretreatment (for example, examples 1 to 4).
Then, from the peak of the temperature differential curve, (i) the half-width (. degree.C.), (ii) the high-temperature-side temperature at the height of 1/10 (value. degree.C.), (iii) the weight reduction rate (weight%) in the low-temperature-side temperature at the height of 7.5/10 of the peak top height, and (iv) the peak top temperature (. degree.C.) were determined, respectively.
(i) Half-peak width (. degree. C.): t isb-Ta
(ii) High temperature side temperature (. degree. C.) ("b value" in Table 1) at 1/10 heights (h/10) of the peak top height h: t isc
(iii) Low temperature side temperature T at height of 7.5/10(7.5h/10) of peak top height hd(weight percent) (the "weight reduction ratio" in table 1): a. the
(iv) Peak top temperature (. degree. C.):Tmax
Tmax: peak temperature (. degree. C.)
DTGmax: temperature TmaxDifferential thermogravimetry of (C) (% v.) (height of peak top h)
Tini: temperature (. degree.C.) at the start of peak
Ta: the value of differential thermogravimetry is DTGmax1/2(h/2) (temperature (. degree. C.) (low temperature side)
Tb: the value of differential thermogravimetry is DTGmax1/2(h/2) at a temperature (. degree.C.) (high temperature side, T)b＞Ta)
Tc: the value of differential thermogravimetry is DTGmax1/10(h/10) at a temperature (. degree.C.) (high temperature side)
Td: the value of differential thermogravimetry is DTGmaxTemperature (. degree.C.) (low temperature side) of 7.5/10(7.5h/10)
A: from TiniTo TdPeak area (peak integral value) in the temperature region of (1)
< surface modification treatability >
0.80g of the obtained fibrous carbon nanostructure (examples 1 to 4: the fibrous carbon nanostructure after the pretreatment, comparative examples 1 to 4: the fibrous carbon nanostructure without the pretreatment), 54.8g of ion-exchanged water, and 83mL of a mixed acid solution containing sulfuric acid (manufactured by Wako pure chemical industries, Ltd., concentration of 96 to 98%) and nitric acid (manufactured by Wako pure chemical industries, Ltd., concentration of 69 to 70%) at a ratio of 1: 3 (volume ratio) were charged into a 300mL flask equipped with a cooling tube and a stirring paddle, and then heated at an internal temperature of 110 ℃ for 8 hours while stirring.
In a 50mL sample bottle, 3.0g of the fibrous carbon nanostructure/mixed acid solution obtained after the mixed acid treatment (which may be referred to as "the present treatment" or "the wet oxidation treatment") was weighed and diluted with 27.0g of ion-exchanged water. After the supernatant liquid was removed, ion-exchanged water was added to make the liquid amount 30 mL. After adding 0.1% ammonia water to adjust the pH to 7.0, the mixture was ultrasonically irradiated at 42Hz for 50 minutes using an ultrasonic irradiation apparatus (Branson Ultrasonics Co., manufactured by Ltd., product name "BRANSON 5510") to obtain a dispersion of fibrous carbon nanostructures.
[ evaluation of Dispersion ]
Then, the obtained dispersion was subjected to 3 cycles of centrifugation at 20000G for 40 minutes and recovery of the supernatant using a centrifugal separator (product name "OPTIMA XL 100K" manufactured by Beckman Coulter inc.) to obtain 20mL of a centrifuged fibrous carbon nanostructure dispersion. The presence or absence of aggregates was visually confirmed in the obtained dispersion.
Further, the absorbance Ab1 (optical path length 1cm, wavelength 550nm) of the dispersion before the treatment with a centrifuge and the absorbance Ab2 (optical path length 1cm, wavelength 550nm) of the dispersion after the treatment with a centrifuge were measured using a spectrophotometer (manufactured by Nissan Spectroscopy, trade name "V670"). The dispersibility of the fibrous carbon nanostructure was evaluated by obtaining the rate of decrease in absorbance by the centrifugal separation treatment according to the following formula. The smaller the absorbance decrease rate (50% or less), the more favorable the surface modification of the fibrous carbon nanostructure, and the more excellent the dispersibility of the fibrous carbon nanostructure.
Absorbance decrease rate (%) {1- (Ab2/Ab1) } × 100
[ evaluation of molded article (film) ]
After the obtained dispersion was applied to a glass substrate by a bar coater #2, the glass substrate was dried at 130 ℃ for 10 minutes to form a film made of a fibrous carbon nanostructure on the glass substrate.
Then, the obtained film was observed with an optical microscope (magnification: 100 times), and the dispersibility of the fibrous carbon nanostructure was evaluated by confirming the presence or absence of aggregates (diameter: 30 μm or more) of the fibrous carbon nanostructure in the field of view of the microscope. The smaller the number of agglomerates of the fibrous carbon nanostructure, the more well the fibrous carbon nanostructure is surface-modified, and the more excellent the dispersibility of the fibrous carbon nanostructure is.
[ comprehensive evaluation ]
The absorbance decrease rate was 50% or less, no aggregates were present in the dispersion, and no aggregates were present in the film, and the film was judged as "good" and the film was judged as "not good".
(example 1)
As an aligned aggregate of fibrous carbon nanostructures (fibrous carbon nanostructures containing CNTs), ZEONANO SG101 manufactured by swiss nano technology corporation, which is a single-walled carbon nanotube, was used. Pretreating a fibrous carbon nanostructure containing the CNT: an oven with an oil-rotary vacuum pump was used and heated at 190 ℃ under vacuum for 15 hours.
Then, the obtained fibrous carbon nanostructure was evaluated for (I) a half-peak width (° c) of a peak of a temperature differential curve, (ii) a high-temperature-side temperature (b value) at a height of 1/10(° c) of a peak top, (iii) a weight reduction rate (wt%) of a low-temperature-side temperature at a height of 7.5/10 of the peak top height, and (iv) a peak top temperature (° c); and (II) surface modification treatability. The results are shown in Table 1.
(example 2)
An aligned aggregate of fibrous carbon nanostructures (a fibrous carbon nanostructure including CNTs) was obtained in the same manner as in example 1, except that in example 1, instead of the pretreatment of heating at 190 ℃ for 15 hours under vacuum, the pretreatment of heating at 120 ℃ for 15 hours under vacuum was performed.
Then, the obtained fibrous carbon nanostructure was evaluated for (I) a half-peak width (° c) of a peak of a temperature differential curve, (ii) a high-temperature-side temperature (b value) at a height of 1/10(° c) of a peak top height, (iii) a weight reduction rate (wt%) in a low-temperature-side temperature at a height of 7.5/10 of the peak top height, and (iv) a peak top temperature (° c); and (II) surface modification treatability. The results are shown in Table 1.
(example 3)
An aligned aggregate of fibrous carbon nanostructures (a fibrous carbon nanostructure including CNTs) was obtained in the same manner as in example 1, except that in example 1, instead of performing the pretreatment of heating at 190 ℃ for 15 hours under vacuum, the pretreatment of heating at 900 ℃ for 6 hours under a nitrogen atmosphere was performed.
Then, the obtained fibrous carbon nanostructure was evaluated for (I) a half-peak width (° c) of a peak of a temperature differential curve, (ii) a high-temperature-side temperature (b value) at a height of 1/10(° c) of a peak top height, (iii) a weight reduction rate (wt%) in a low-temperature-side temperature at a height of 7.5/10 of the peak top height, and (iv) a peak top temperature (° c); and (II) surface modification treatability. The results are shown in Table 1.
(example 4)
An aligned assembly of fibrous carbon nanostructures (CNT-containing fibrous carbon nanostructures) was obtained in the same manner as in example 1, except that in example 1, instead of the pretreatment of heating at 190 ℃ for 15 hours under vacuum, the pretreatment of heating at 800 ℃ for 6 hours under a nitrogen atmosphere was performed.
Then, with respect to the obtained fibrous carbon nanostructure, (I) the half-peak width (° c) of the peak of the temperature differential curve, (ii) the high-temperature-side temperature (b value) at the height of 1/10(° c) of the peak top height, (iii) the weight reduction rate (wt%) of the low-temperature-side temperature at the height of 7.5/10 of the peak top height, and (iv) the peak top temperature (° c) were evaluated; and (II) surface modification treatability. The results are shown in Table 1.
Comparative example 1
"ZEONANO SG 101", manufactured by zeono nanotechnology corporation, which is a single-layer carbon nanotube as an oriented aggregate of fibrous carbon nanostructures (fibrous carbon nanostructures including CNTs) that was not subjected to a pretreatment of heating under vacuum, was evaluated for (I) a half-peak width (° c) of a peak of a temperature differential curve, (ii) a high-temperature-side temperature (b value) at a height of 1/10 of a peak top height (° c), (iii) a weight reduction rate (weight%) of a low-temperature-side temperature at a height of 7.5/10 of the peak top height, and (iv) a peak top temperature (° c); and (II) surface modification treatability. The results are shown in Table 1.
Comparative example 2
In comparative example 1, an oriented aggregate of fibrous carbon nanostructures (fibrous carbon nanostructure including CNTs) was evaluated for (I) a half-peak width (° c) of a peak of a temperature differential curve, (ii) a high-temperature-side temperature (b value) at a height of 1/10(° c) of a peak top height, (iii) a weight reduction rate (wt%) of a low-temperature-side temperature at a height of 7.5/10 (c) of the peak top height, and (iv) a peak top temperature (° c), in the same manner as in comparative example 1, except that "tubal" manufactured by arcial corporation, which is a single-walled carbon nanotube of an oriented aggregate of fibrous carbon nanostructures, was used; and (II) surface modification treatability. The results are shown in Table 1.
Comparative example 3
Except for using Signis SG-65I of single-walled carbon nanotubes as aligned aggregates of fibrous carbon nanostructures in comparative example 1, the same procedure as in comparative example 1 was repeated, and (I) the half-peak width (° c) of the peak of the temperature differential curve, (ii) the high-temperature-side temperature (b value) (° c) at a height of 1/10 from the peak top, (iii) the rate of weight reduction (wt%) at the low-temperature-side temperature at a height of 7.5/10 from the peak top height, and (iv) the peak top temperature (° c) were evaluated for aligned aggregates of fibrous carbon nanostructures (CNTs-containing fibrous carbon nanostructures); and (II) surface modification treatability. The results are shown in Table 1.
Comparative example 4
Except for using "MEIJO edps EC 1.5" manufactured by the famous nano carbon company of single-walled carbon nanotubes as an oriented aggregate of fibrous carbon nanostructures in comparative example 1, an oriented aggregate of fibrous carbon nanostructures (fibrous carbon nanostructures including CNTs) was evaluated for (I) a half-peak width (° c) of a peak of a temperature differential curve, (ii) a high-temperature-side temperature (b value) at a height of 1/10(° c) of a peak top height, (iii) a weight reduction rate (weight%) of a low-temperature-side temperature at a height of 7.5/10(° c) of a peak top height, and (iv) a peak top temperature (° c) in the same manner as in comparative example 1; and (II) surface modification treatability. The results are shown in Table 1.
[ Table 1]
Figure BDA0003144018790000151
As is clear from table 1, the fibrous carbon nanostructures of examples 1 to 4 were surface-modified well and had excellent dispersibility (overall evaluation was "excellent") as compared with the fibrous carbon nanostructures of comparative examples 1 to 4.
Industrial applicability
According to the present invention, a fibrous carbon nanostructure that can be easily subjected to surface modification treatment and a method for producing the same can be provided.
Further, according to the present invention, a method for producing a surface-modified fibrous carbon nanostructure, which is surface-modified satisfactorily, can be provided.
Description of the reference numerals
Tmax: peak temperature (. degree. C.)
DTGmax: temperature TmaxDifferential thermogravimetry of (C) (% v.) (height of peak top h)
Tini: temperature (. degree.C.) at the start of peak
Ta: the value of differential thermogravimetry is DTGmax1/2(h/2) (temperature (. degree. C.) (low temperature side)
Tb: the value of differential thermogravimetry is DTGmax1/2(h/2) at a temperature (. degree.C.) (high temperature side, T)b＞Ta)
Tc: the value of differential thermogravimetry is DTGmax1/10(h/10) at a temperature (. degree.C.) (high temperature side)
Td: the value of differential thermogravimetry is DTGmaxTemperature (. degree.C.) (low temperature side) of 7.5/10(7.5h/10)
A: from TiniTo TdPeak area (peak integral value) in the temperature region of (1)

Claims (7)

1. A fibrous carbon nanostructure having a half-peak width of a peak of a temperature differential curve of a first order differential curve of a thermogravimetric curve obtained by thermogravimetric analysis in a dry air environment of 38 ℃ or more and less than 90 ℃,
the high temperature side temperature at the height 1/10 of the peak top height of the peak is 658 ℃ or higher.
2. The fibrous carbon nanostructure according to claim 1, wherein a weight reduction rate of the low-temperature-side temperature at a height of 7.5/10 of a peak top height of the peak is 40 wt% or less.
3. The fibrous carbon nanostructure according to claim 1 or 2, wherein the peak top temperature of the peak is 530 ℃ or more and less than 730 ℃.
4. A method for producing a fibrous carbon nanostructure, which is the method for producing a fibrous carbon nanostructure according to any one of claims 1 to 3,
the method for producing a fibrous carbon nanostructure includes a step of heating the fibrous carbon nanostructure to a temperature of 120 ℃ or higher in a vacuum environment.
5. A method for producing a fibrous carbon nanostructure, which is the method for producing a fibrous carbon nanostructure according to any one of claims 1 to 3,
the method for producing a fibrous carbon nanostructure includes a step of heating the fibrous carbon nanostructure to a temperature of 800 ℃ or higher in an inert gas atmosphere.
6. A method for producing a surface-modified fibrous carbon nanostructure, comprising a step of subjecting the fibrous carbon nanostructure according to any one of claims 1 to 3 to a surface modification treatment to obtain a surface-modified fibrous carbon nanostructure.
7. The method for producing a surface-modified fibrous carbon nanostructure according to claim 6, wherein the surface modification treatment is a wet oxidation treatment.
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